N-alkoxyalkylidenesulfonamide compounds as herbicides

ABSTRACT

THE PRESENT INVENTION IS DIRECTED TO NOVEL COMPOUNDS OF THE FORMULA   1-(R1-N(-R2)-),2,6-DI(O2N-),4-(R4O-C(-R3)=N-SO2-)-BENZENE   WHICH COMPOUNDS ARE USEFUL AS HERBICIDES. IN THE ABOVE AND SUCCEEDING FORMULAE HEREIN, R1 REPRESENTS HYDROGEN OR R2, AND EACH R2 INDEPENDENTLY REPRESENTS LOWERALKYL OF C1-C4, LOWERALKENYL OF C3-C4, LOWERALKYNYL OF C3-C4, OR RADICAL OF THE FORMULA -CH2--CH2$CH2$NY, WHEREIN N REPRESENTS 0 TO 1, AND Y REPRESENTS METHOXY, CYANO, BROMO, OR CHLORO, SUBJECT TO THE LIMITATION THAT THE GROUPS REPRESENTED BY R1 AND R2 TOGETHER CONTAIN FROM 2 TO 8, BOTH INCLUSIVE, CARBON ATOMS; R3 REPRESENTS HYDROGEN, LOWERALKYL OF C1-C2, OR PHENYL; AND R4 REPRESENTS ALKYL OF C1-C8, ALLYL, OR 2-CHLOROETHYL.

United States Patent 3,832,155 N-ALKOXYALKYLIDENESULFONAMIDE COMPOUNDS AS HERBICIDES James R. Beck, Indianapolis, Ind., assignor to Eli Lilly and Company, Indianapolis, Ind.

No Drawing. Original application Nov. 3, 1970, Ser. No. 86,619, now Patent No. 3,681,406. Divided and this application Mar. 6, 1972, Ser. No. 232,288

Int. Cl. A01n 9/14 U.S. Cl. 71-103 13 Claims ABSTRACT OF THE DISCLOSURE The present invention is directed to novel compounds of the formula which compounds are useful as herbicides. In the above and succeeding formulae herein, R represents hydrogen or R and each R independently represents loweralkyl of C -C loweralkenyl of C -C loweralkynyl of C -C or radical of the formula -CH CH {-CH -),,Y, wherein n represents 0 or 1, and Y represents methoxy, cyano, bromo, or chloro, subject to the limitation that the groups represented by R and R together contain from 2 to 8, both inclusive, carbon atoms; R represents hydrogen, loweralkyl of C -C or phenyl; and R represents alkyl of C -C allyl, or 2-chloroethyl.

This is a division of application Ser. No. 86,619 filed Nov. 3, 1970 and issued Aug. 1, 1972 as U.S. Pat. 3,681,- 406.

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to novel herbicidal compounds of the formula NO: R a

R O R N03 wherein R R R and R are as defined hereinabove. The compounds are prepared by the reaction of a 3,5-dinitro-N ,N -R ,R -sulfanilamide, of the formula with an ortho ester of the formula R -C{-OR The reaction goes forward over a wide range of temperatures, but for good yields should be carried out at a temperature range of from 100 to 200 C. The reaction consumes the reactants in amounts representing equimolecular amounts, but an excess of the ortho ester serves additionally as reaction medium and assures higher yields; hence the use of excess ortho ester is preferred. The reaction yields the desired product of the present invention as well as by-product of the formula R OH. Separation and, if desired, purification, are carried out in conventional procedures.

3,832,155 Patented Aug. 27, 1974 Aliphatic groups unless otherwise specified are straightchain.

The synthesis of the compounds of the present invention is illustrated by the following examples.

EXAMPLE 1 N l-Ethoxyethylidene) -3 ,5-Dinitro N ,N -Dipropylsulfanilamide 3,5 Dinitro-N ,N -dipropylsulfanilamide (35.0 grams;

0.1 mole) and milliliters of triethyl orthoacetate (about 0.4 mole) were mixed and the mixture heated to C. and maintained at 100 C. for two and one-half hours. Nitrogen was blown in for the last one-half hour. The reaction mixture was then cooled to room temperature, about 150 milliliters of ether added, and the mixture filtered. The filtrate was concentrated on a steam bath, whereupon the desired N l-ethoxyethylidene) 3,5 dinit'ro N ,N dipropylsulfanilamide product crystallized. The product so obtained melted at 73-4 C.

Analysis.Calc.: C, 46.15; H, 5.81; N, 13.46. Found: C, 46.37; H, 5.75; N, 13.68.

EXAMPLES 2-15 -In accordance with the foregoing teachings and with the procedures of Example 1, but employing appropriate other starting materials, the following other compounds of the present invention were prepared.

N l-butoxyethylidene) -3,5-dinitro-N ,N -dipropylsulfanilamide, m.p., 4l-4 C.

N -isobutoxymethylene-3,5-dinitro-N ,N -dipropylsulfanilamide, m.p., 856 C.

N (a-ethoxybenzylidene -3 ,5 -dinitro-N ,N -dipropylsulfanilamide, m.p., 106-7 C.

N l-methoxyethylidene -3,5-dinitro-N ,N -dipropylsulfanilamide, m.p., 96-7 C.

N 1-ethoxypropylidene)-3, 5-dinitro-N ,N -dipropylsulfanilamide, m.p., 4950 C.

N (2-chloroethoxymethylene) -3 ,5 -dinitro -N ,N -dipropylsulfanilamide, m.p., -6 C.

N -butoxymethylene-3,5-dinitro-N ,N -dipropy1- sulfanilamide, m.p., 71-2 C.

N -propoxymethylene-3,5-dinitro-N ,N -dipropylsulfanilamide, m.p., 945 C.

N (a-methoxybenzylidene) -3,5-dinitro-N ,N -dipropylsul-fam'lamide, m.p., 121-23 C.

N l-methoxypropylidene -3,5-dinitro-N ,N -dipropylsulfanilamide, m.p., 64-5 C.

N -allyloxymethylene-3,5-dinitro-N ,N -dipropylsulfanilamide, m.p., 77-8 C.

N 2-ethylhexyloxymethylene) -3,5-dinitro-N ,N -dipropylsulfanilamide, an oil. 7

N -ethoxymethylene-3,5-dinitro-N ,N -dipropylsulfanilamide, m.p., 11'4-15 C.

N -methoxymethylene-3,'5-dinitro-N ,N -dipropy1- sulfanilamide, m.p., 77-8 C.

EXAMPLES 16-25 Yet other representative compounds illustrative of the present invention are the following:

N -methoxymethylene-3,5-dinitro-N ,N -dimethylsulfanilamide The compounds of the present invention are adapted to be employed as herbicides. The compounds can be utilized to achieve broad herbicidal action; hence, in its broadest sense, the present invention is directed to a method which comprises applying to a plant part, which can be a stem, leaf, flower, fruit, root, or seed or other similar reproductive unit of a plant, a growth-inhibiting amount of one of the compounds of the present invention. However, the compounds can also be utilized to take advantage of selective patterns of herbicidal activity.

It is not critical to the practice of the present invention that complete destruction of undesirable vegetation be obtained, it being adequate if the growth of the unwanted vegetation is merely inhibited. Especially where selective action is sought, inhibition falling short of actual killing is adequate, particularly when combined with naturally occurring conditions such as limited moisture and the like which more adversely affect the vegetation selectively inhibited than the crop plant.

The compounds of the present invention are suited to a wide variety of herbicidal applications. Thus, for example, at rates which evoke the selective action of the compounds, which rates are defined more completely hereinbelow, the compounds can be used as selective herbicides in crop plants, such as, for example, cotton, corn, sorghum, soybeans, and the like. In such use, application can be made preemergent to both crops and weeds, or, preferably by means of a directed spray application technique, postemergent to the crop plant but both preemergent and post-emergent to the weeds. In another application, the compounds can be used to give broad herbicidal action on non-crop land, including intermittently non-crop strips of contour-farmed land. For such usage on so-called fallow land, application can be made in spring to suppress vegetative growth until a fall or following spring planting, or in the fall to suppress vegetative growth until a spring or following fall planting. Furthermore, in another application, the present compounds can be utilized to control weeds in tree crop plantings, such as plantings of the various citrus trees. Also, the compounds can be used for turf applications. In all of these various applications, and yet others for which the present compounds are suited, another advantage is that the compounds need not be disced into the soil being treated, it being adequate if one of the compounds, or a formulation containing one of the compounds, is merely spread onto the top surface. However, where desired or convenient, the compounds can be disced into, or otherwise mechanically mixed with the soil. In addition to the foregoing terrestrial embodiments, the present compounds can also be utilized as aquatic herbicides.

The practice of the present invention in any of its numerous embodiments can in some instances be carried out with unmodified compound; however, for good results, it is generally necessary that the compound be em- 4 ployed in modified form, that is, as one component of a composition formulated to implement the plant growthinhibiting effects. Thus, for example, the active agent can 'be mixed with water or other liquid or liquids, preferably aided by the usage of a surface active agent. The active agent can also be incorporated on a finely divided solid, which can be a surface active substance, to yield a Wettable powder, which can subsequently be dispersed in water or other liquid, or incorporated as part of a dust which can be applied directly. Other methods of formulations are known in the art and can be emplgyed in implementing the present invention. v.

In carrying out the novel methodof the present invention, the exact amount of the active agent employed'is not critical and will vary, depending upon the type of growth-inhibiting effect desired, the identity, of the plants concerned, the particular active agent used, weather conditions, and the like. In general, a broad growth-inhibiting effect is obtained with rates of from about 8 to 20 pounds or more of active agent per acre, and such rates are suitable and effective for control of vegetative growth on fallow land. When it is desired to obtain a selective growth-inhibiting effect on weeds in areas containing crop plants, such as corn, soybeans, and cotton, rates of from 0.125 to 8.0 pounds generally give good results. When in the typical mode of operation, the activeagent isemployed as a composition Comprising the agent, the exact concentration of active agent in the composition .is not critical, except that the concentration and total amount of formulation employed be adequate to supply the appropriate amount of active agent on a per acre basis. In general, good results are obtained when employing formulations containing the active agent in a concentration of from 0.5 to 10 percent or higher, in the instance of a liquid formulation; and in a concentration of from, 1.0 to 5.0 percent or higher, in the instance of a dust, powder, granule, or the like. More concentrated formulations can be prepared and are often preferred in that they can serve, depending upon the particular application contemplated and the particular concentration, both as a concentrated formulation for purposes of shipment, storage, and the like, and as an ultimate treating composition. Thus, for example, formulations often preferably contain a surface active agent and the present active agent, the latter being present in an amount of from 0.5 to 99.5 percent, by weight; or an inert, finely divided solid and the present active agent, the latter being present in an amount of from 1.0 to 99.0 percent, by weight. Such formulations, as indicated, can be employed directly in certain applications, but can also be diluted and subsequently employed in many other applications.

Liquid compositions containing the desired amount of active agent are prepared by dissolving the .substance in a liquid, with or without the aid of a surface active dispersing agent such as an ionic or non-ionic emulsifying agent. Suitable liquids include agricultural spray oils and the petroleum distillates such as xylene, diesel fuel, kerosene, fuel oil naphthas and Stoddard solvent. The choice of dispersing and emulsifying agent and the amount thereof employed is dictated by the nature of the composition and by the ability of the agent to facilitate the dispersion of the active agent in the carrier to produce the desired composition. Dispersing and emulsifying agents which can be employed in the compositions include the condensation products of alkylene oxides with phenols and organic acids, alkyl aryl sulfonates, pol'yoxy- 'alkylen'e derivatives or sorbitan esters, complex ether alcohols, and the like. Representative surface active agents which are suitably employed in implementing the present mvention are identified in US. Pats. 3,095,299, second column, lines 25-36, 2,655,447, column 5, and 2,412,510, columns 4 and 5.

In the preparation of dust compositions, the active ingredient is intimately dispersed in and on a finely divided solid such as clay, talc, chalk, gypsum, limestone, vermiculite fines, perlite, and the like. In one method of achieving such dispersion, the finely divided carrier is mechanically mixed or ground with the active agent.

Similarly, dust compositions containing the toxicant compounds can be prepared with various of the solid surface active dispersing agents such as bentonite, fullers earth, attapulgite and other clays. Depending upon the proportions of ingredients, these dust compositions can be employed as concentrates and subsequently diluted with additional solid surface active dispersing agents or with chalk, talc, or gypsum and the like to obtain thedesired amount of active ingredient in a composition adapted to be employed for the suppression of the growth'of the plants. Also, such dust compositions can be dispersed in water, with or without the aid of a dispersing agent, to form spray mixtures.

Formulations containing the present active agent are often advantageously further modified by incorporation therein of an effective amount of a surfactant which facilitates the dispersion and spreading of the formulation H of the plant leaf surfaces and the incorporation of the formulation by the plant.

In accordance with the present invention, the active agent can be dispersed in soil or other growth media in any convenient fashion. Applications can be carried out by simply mixing with the media, by applying to the surface of soil and thereafter dragging or discing into the soil to the desired depth, or by employing a liquid carrier to accomplish the penetration and impregnation. The application of spray and dust compositions to the surface of soil, or to plant parts or the above ground surfaces of plants can be carried out by conventional methods, e.g., powder dusters, boom and hand sprayers and spray dusters, whether surface or air-borne. However, while such conventional modes of application can be used, they are not required. As above noted, it is an advantage of the present invention that the compounds serving as active agent are active'and effective as herbicides when merely placed on the surface of the soil, without any additional step to assist incorporation. Thus, the compounds are of substantially the same efficacy regardless of Whether they are applied to the surface only, or whether they are applied to the surface and subsequently disced into the soil.

In a further method, the distribution of the active agent in soil can be accomplished by introducing the agent into the water employed to irrigate the soil. In such procedures, the amount of water is varied with the porosity and waterholding capacity of the soil to obtain a desired depth of distribution of the agent.

In addition, the present method also comprehends the employment of an aerosol composition containing one or more of the present active agents as an active compound. Such a composition is prepared according to conventional methods wherein the agent is dispersed in a solvent, and the resultant dispersion mixed with a propellant in liquid state. Such variables as the particular agent to be used and the nature of the vegetation which is to be treated will determine the desirability of the solvent and concentration of the agent therein.

vention for the purpose of conducting the herbicidal evalnation, the results ofwhich' are reported hereinbelow,

cedures. The compound to be evaluated was initially suspended in a 1:1 acetone/ethanol solution of a blend of nonionic sulfonate emulsifying agents. The suspension was then diluted with an aqueous solution of the same blend of agents to obtain the ultimate treating composition; this composition contained 4.15 percent of each of the acetone and ethanol, 1000 p.p.m. of the blend of emulsifying agents, and the respective compounds in an amount to supply the desired pounds per acre. In the instance of some of the lower rates, a formulation so obtained was further diluted with water containing 1000 p.p.m. of the blend of emulsifying agents, only, thus further lessening the concentration of the ethanol and acetone.

EXAMPLES 27-41 Various of the compounds of the present invention were evaluated for preemergent application to various species of plants. In this evaluation, a soil was prepared consisting of one part masonry sand and one part shredded top soil blended together in a cement mixer. One gallon of this soil was placed in a 21.5 X 31.5 cm. galvanized fiat and was patted down with a bench brush until level. A three-row marker was used to make 2 /2 cm. deep furrows in approximately two-fifths of the flat. Cropseeds consisting of four kernels of corn, five cotton seeds and five soybean seeds were placed in these furrows. A four-row template was then placed on the remaining soil and'th'e indicated approximate numbers of each of the following seeds were planted, one species to each section: .foxtail (millet), -100 seeds; velvetleaf (40-50 seeds); rough pigziveed (l50250 seeds); and large crabgrass (-150 see s).

Suflicient soil was added to cover the entire flat. Thus, the weed seeds were covered to a depth of about 6 mm. and the crop seeds were covered to a depth of about 3 cm.

In assaying the effect of a compound as a preemergen t herbicide, a flat prepared as above, taken either on the day of planting or on the next day, wasplaced in a chamber equipped with a turntable and an air exhaust.

A herbicidal composition containing the compound prepared as described in the preceding example was applied to the flat with a modified DeVilbiss atomizer hooked to an air source. Twelve and one-half milliliters of the composition under test were applied to each flat either on the day of planting or on the succeeding day. Injury ratings and observations as to type of injury were made eleven to twelve days after treatment. The injury rating scale used was as follows:

0--no injury l-slight injury 2moderat'e injury 3severe injury 4death When more than one determination was carried out at a givenrate, an average value was calculated forthe inury rat ng. a

In the following table setting forth the results of the evaluation, column 1 gives the name of the compounds under test; column 2, the rate in pounds per acre at which the compound was applied to the test fiat; and theremaining columns, the injury to the particular plant seeds was carried out in accordance with conventional pro- 65 or seedlings as measured by the foregoing scale.

TABLE I Injury rating on preemergent treatment;

Lbs.l Soy- Orab- Pi Fox- V t- Compound acre Corn Cotton bean grass w'ee l tail- 'lZaf N -(l-butoxyethylidene)-3,5-dinitro-N ,N -dipropylsulfanilamide 8 2 1 1 4 I N -isobutoxymethylene-3,5dinitro-N ,N -dipropylsulfanilamide 8 2 2 2 4 4 Fox- Volvettail leaf Soy- Crab- Pigbean grass Weed TABLE I-Contiuued Lbs./

acre Corn Cotton Compound u 232 221 2 22 32 2 n 322 3253 22 n 2 q u 233 335 3333 3333 435 333 3 333 333 2 2 4 3 44 .4. .3 4444 44 4 445 4.35 44 3 .43 4442 4.44. 445 3 2 a a 34 4 445 4355 4443 444 44 5 43:0 435 444 4 455 44 54 333 5 3 3 3 3 3 3 33 3 3 100 111 2015 1155 21 5 1.00 105 210 0.155 226 125 201 0 1O 0 0 Q0 0 0 100 125 2055 1000 203 000 000 100 100 1001 1150 120 2 0 0 0 0 115 100 2000 0055 105 210 00 110 210 1110 2153 125 200 0 0 Q 0 0 0 842 84 2 84 21 84 8 2 842 42 842 842 84 21 3421 842 N -(a-ethoxybeuzylldene) 3,5-dinitro-N ,N -dipropylsulfanilamldo N -(l-mathoxyethylldene) -3,5-dinitro-N ,N -dipropylsulianilamido.

N -(l-ethoxypropylldene) -3,5-d.lnitro-N ,N -dipropylsultanilamida-.

N -(2;ghloroetl1oxymethy1ene) -3,5-dinitro-N ,N -dipropylsulfani1amide am fl N -butoxymethylenebfi dinltro-N ,N -dipropy1sulfani1amide.

N -propoxymethylene-3,5-dinltro-N,N -dlpropylsullanilamide- N -(a-methoxybenzylidene)3,5-dlnltro-N ,N -dipropylsull'anilami do.

N -(l-methoxypropylidene-3,5-din1tro-N ,N -dipropylsulfanilamiden.

N -al1yloxymethylene-B,5-dlnitro-N ,N dipropylsulfanilamide- N -(Z-ethylhexyloxymethylene)-3,5-dinitro-NfilW-dipropylsulfanilaml (in N -ethoxymethylene-3,5-dinitr0-N,N-dipr0py1sulianilamide N -(l-ethoxyethylldene) -3,5-dln1tro-N ,N -dlpropylsull'anllamlde.

N -metboxymethy1ene-3,5-dinltr0-N ,N -dlpropylsultanilamide.

ER C{OR are in many instances commercially available. However, all of the compounds can be synthesized in accordance with known procedures: see, e.g., Wagner and look,

-SO;NH1

are in many instances known compounds-see US. Pat. 3,367,949. Those compounds not expressly covered by the scope of this patent are prepared in like manner, by reaction of an appropriately substituted 4-amin0-3,5- 65 dinitrobenzenesulfonyl halide with ammonium hydroxide.

a S02N=C OR NO:

The ortho esters to be employed as starting materials 45 in accordance with the present invention:

Synthetic Organic Chemistry (John Wiley & Sons, New York, 1965), chapter 16 and references there cited. The 3,4-dinitro-N ,N -R ,R -sulfanilamide compounds to be employed in the preparation of the compounds of the present invention I claim: 1. The method which comprises applying to a plant part a growth-inhibiting amount of an active agent, said active agent being a compound of the formula EXAMPLES 42-51 Essentially the same results as those reported in foregoing Examples 27-41 are obtained when evaluating the sulfanilamide N -ethoxymethylene-3,5-dinitro-N -ethyl-N -butylsulfanilamide N l-methoxypropylidene) -3,5-dinitro-N ,N

diallylsulfanilamide N l-ethoxyethylidene) -3,5-dinitroN ,N -dipropynylsulfanilamide N -penty1oxymethylene-3,5-dinitro N ,N -bis(2- methoxyethyl) sulfanil amide N l-methoxypropylidene) -3,5-dinitro-N ,N bis- (Z-bromoethyl sulfanilamide N -mcthoxymethylene-3,5-diuitro-N -isopropylsulfanilamide N -methoxymethylene-3,5-dinitro-N ,N -bis(3-methoxypropyl)sulfanilamide N -methoxymethylene-3,5-dinitro-N ,N bis(3- chloropropyl)sulfanilamide N l-methoxyethylidene) -3, 5-dinitro N ,N -bis- (Z-cyanoethyl)sulfanilamide Satisfactory results are obtained when the active agent of the present invention, or a composition comprising such active agent, is combined with other agricultural materials intended to be applied to plants, plant parts, or

following other representative compounds of the present invention. N -methoxymethylene-3,5-dinitroaN ,N -dimethyltheir habitats. Such materials include fertilizers, fungicides, nematocides, insecticides, other herbicides, soil conditioning agents, and the like.

wherein R represents hydrogen or R and each R independently represents loweralkyl of C -C loweralkenyl of C -C loweralkynyl of C -C or radical of the formula CH -CH -CH Y, wherein n represents or 1, and Y represents methoxy, cyano, bromo, or chloro, subject to the limitation that the groups represented by R and R together contain from 2 to 8, both inclusive, carbon atoms; R represents hydrogen, loweralkyl of C C or phenyl; and R represents alkyl of C -C allyl, or 2- chloroethyl.

2. The method of Claim 1 wherein the active agent is N -(1 methoxyethylidene) 3,5 dinitro-N ,N -dipropy1- sulfanilamide.

3. The method of Claim 1 wherein the active agent is N ethoxymethylene-3,5-dinitro-N ,N -dipropylsulfanilamide.

4. The method of Claim 1 wherein the active agent is N (1 ethoxyethylidene)-3,5-dinitro-N ,N -dipropylsulfanilamide.

5. The method of Claim 1 wherein the active agent is N (1 methoxypropylidene)-3,5-dinitro-N ,N -dipropylsulfanilamide.

6. The method of Claim 1 wherein the active agent is N -methoxymethylene-3,5-dinitro-N ,N -dipropylsulfanilamide.

7. The composition suitable for effecting plant growth inhibition which comprises a surface active agent and a plant growth inhibiting amount of an active agent which is a compound of the formula R O R Nor wherein R represents hydrogen or R and each R independently represents loweralkyl or C -C loweralkenyl of C -C loweralkynyl of C -C or radical of the formula CH CH {-CH -},,Y, wherein n represents 0 to 1, and Y represents methoxy, cyano, bromo, or chloro, subject to the limitation that the groups represented by R and R together contain from 2 to 8, both inclusive, carbon atoms; R represents hydrogen, loweralkyl of C -C or phenyl; and R represents alkyl of C -C allyl, or 2- chloroethyl.

8. The composition of Claim 7 wherein the active agent is N (l-methoxyethylidene)3,S-dinitro-NfllB-dipropylsulfanilamide.

wherein R represents hydrogen or R and each R independently represents loweralkyl of C -C loweralkenyl EOf C -C loweralkynyl of C -C or radical of the formula CH CH {-CH )nY, wherein n represents 0 or 1, and Y represents methoxy, cyano, bromo, or chloro, subject to the limitation that the groups represented by R and R together contain from 2 to 8, both inclusive, carbon atoms; R represents hydrogen, loweralkyl of C -C or phenyl; and R represents alkyl of C -C allyl, or 2- chloroethyl.

References Cited UNITED STATES PATENTS 3,367,949 2/1968 SOper 71--103 3,471,436 10/1969 Collins 71-103 3,653,873 4/1972 Bayer 71-103 3,717,690 2/1973 Newman 71103 JAMES O. THOMAS, JR., Primary Examiner US Cl. X.R. 

